Quantifying Chemical Reactions and Interfacial Properties at Buried Polymer/Polymer Interfaces.

Maleic anhydride (MAH)-modified polymers are used as tie layers for binding dissimilar polymers in multilayer polymer films. The MAH chemistry which promotes adhesion is well characterized in the bulk; however, only recently has the interfacial chemistry been studied. Sum frequency generation vibrational spectroscopy (SFG) is an interfacial spectroscopy technique which provides detailed information on interfacial chemical reactions, species, and molecular orientations and has been essential for characterizing the MAH chemistry in both nylon and ethyl vinyl alcohol copolymer (EVOH) model systems and coextruded multilayer films. Here, we further characterize the interfacial chemistry between MAH-modified polyethylene tie layers and both EVOH and nylon by investigating the model systems over a range of MAH concentrations. We can detect the interfacial chemical reaction products between MAH and the barrier layer at MAH concentrations of ≥0.022 wt % for nylon and ≥0.077 wt % for EVOH. Additionally, from the concentration-dependent reaction reactant/product SFG peak positions and the product imide or ester/acid C═O group tilt angles extracted from the polarization-dependent SFG spectra, we quantitatively observe concentration-dependent changes to both the interfacial chemistry and interfacial structure. The interfacial chemistry and molecular orientation as a function of MAH concentration are well correlated with the adhesion strength, providing important quantitative information for the future design of MAH-modified tie layers for a variety of important applications.

Elucidating the Changes in Molecular Structure at the Buried Interface of RTV Silicone Elastomers during Curing.

Silicone elastomers are widely used in many industrial applications, including coatings, adhesives, and sealants. Room-temperature vulcanized (RTV) silicone, a major subcategory of silicone elastomers, undergoes molecular structural transformations during condensation curing, which affect their mechanical, thermal, and chemical properties. The role of reactive hydroxyl (-OH) groups in the curing reaction of RTV silicone is crucial but not well understood, particularly when multiple sources of hydroxyl groups are present in a formulated product. This work aims to elucidate the interfacial molecular structural changes and origins of interfacial reactive hydroxyl groups in RTV silicone during curing, focusing on the methoxy groups at interfaces and their relationship to adhesion. Sum frequency generation (SFG) vibrational spectroscopy is an in situ nondestructive technique used in this study to investigate the interfacial molecular structure of select RTV formulations at the buried interface at different levels of cure. The primary sources of hydroxyl groups required for interfacial reactions in the initial curing stage are found to be those on the substrate surface rather than those from the ingress of ambient moisture. The silylation treatment of silica substrates eliminates interfacial hydroxyl groups, which greatly impact the silicone interfacial behavior and properties (e.g., adhesion). This study establishes the correlation between interfacial molecular structural changes in RTV silicones and their effect on adhesion strength. It also highlights the power of SFG spectroscopy as a unique tool for studying chemical and structural changes at RTV silicone/substrate interface in situ and in real time during curing. This work provides valuable insights into the interfacial chemistry of RTV silicone and its implications for material performance and application development, aiding in the development of improved silicone adhesives.

Molecular behavior of silicone adhesive at buried polymer interface studied by molecular dynamics simulation and sum frequency generation vibrational spectroscopy.

Silicones have excellent material properties and are used extensively in many applications, ranging from adhesives and lubricants to electrical insulation. To ensure strong adhesion of silicone adhesives to a wide variety of substrates, silane-based adhesion promotors are typically blended into the silicone adhesive formulation. However, little is known at the molecular level about the true silane adhesion promotion mechanism, which limits the ability to develop even more effective adhesion promoters. To understand the adhesion promotion mechanism of silane molecules at the molecular level, this study has used sum frequency generation vibrational spectroscopy (SFG) to determine the behavior of (3-glycidoxypropyl)trimethoxy silane (γ-GPS) at the buried interface between poly(ethylene terephthalate) (PET) and a bulk silicone adhesive. To complement and extend the SFG results, atomistic molecular dynamics (MD) simulations were applied to investigate molecular behavior and interfacial interaction of γ-GPS at the silicone/PET interface. Free energy computations were used to study the γ-GPS interaction in the sample system and determine the γ-GPS interfacial segregation mechanism. Both experiments and simulations consistently show that γ-GPS molecules prefer to segregate at the interface between PET and PDMS. The methoxy groups on γ-GPS molecules orient toward the PDMS polymer phase. The consistent picture of interfacial structure emerging from both simulation and experiment provides enhanced insight on how γ-GPS behaves in the silicone - PET system and illustrates why γ-GPS could improve the adhesion of silicone adhesive, leading to further understanding of silicone adhesion mechanisms useful in the design of silicone adhesives with improved performance.

Molecular Interactions between Amino Silane Adhesion Promoter and Acrylic Polymer Adhesive at Buried Silica Interfaces.

In this study, the influence of an amino silane (3-(2-aminoethylamino)-propyldimethoxymethylsilane, AEAPS) on the interfacial structure and adhesion of butyl acrylate/methyl methacrylate copolymers (BAMMAs) to silica was investigated by sum frequency generation vibrational spectroscopy (SFG). Small amounts of methacrylic acid, MAA, were included in the BAMMA polymerizations to assess the impact of carboxylic acid functionality on the glass interface. SFG was used to probe the O-H and C═O groups of incorporated MAA, ester C═O groups of BAMMA, and CH groups from all species at the silica interfaces. The addition of AEAPS resulted in a significant change in the molecular structure of the polymer at the buried interface with silica due to specific interactions between the BAMMA polymers and silane. SFG results were consistent with the formation of ionic bonds between the primary and secondary amines of the AEAPS tail group and the MAA component of the polymer, as evidenced by the loss of the MAA O-H and C═O signals at the interface. It is extensively reported in the literature that methoxy head groups of an amino silane chemically bind to the silanols of glass, leaving the amine groups available to react with various chemical functionalities. Our results are consistent with this scenario and support an adhesion promotion mechanism of amino silane with various aspects: (1) the ionic bond formation between the tail amine group and acid functionality on BAMMA, (2) the chemical coupling between the silane head group and glass, (3) migration of more ester C═O groups to the interface with order, and (4) disordering or reduced levels of CH groups at the interface. These results are important for better understanding of the mechanisms and effect of amino silanes on the adhesion between acrylate polymers and glass substrates in a variety of applications.

Probing Covalent Interactions at a Silicone Adhesive/Nylon Interface.

Covalent bonding is one of the most robust forms of intramolecular interaction between adhesives and substrates. In contrast to most noncovalent interactions, covalent bonds can significantly enhance both the interfacial strength and durability. To utilize the advantages of covalent bonding, specific chemical reactions are designed to occur at interfaces. However, interfacial reactions are difficult to probe in situ, particularly at the buried interfaces found in well-bonded adhesive joints. In this work, sum frequency generational (SFG) vibrational spectroscopy was used to directly examine and analyze the interfacial chemical reactions and related molecular changes at buried nylon/silicone elastomer interfaces. For self-priming elastomeric silicone adhesives, silane coupling agents have been extensively used as adhesion promoters. Here with SFG, the interfacial chemical reactions between nylon and two alkoxysilane adhesion promoters with varied functionalities (maleic anhydride (MAH) and epoxy) formulated into the silicone were observed and investigated. Evidence of reactions between the organofunctional group of each silane and reactive groups on the polyamide was found at the buried interface between the cured silicone elastomer and nylon. The adhesion strength at the nylon/cured silicone interfaces was substantially enhanced with both silane additives. SFG results elucidated the mechanisms of organo-silane adhesion promotion for silicone at the molecular level. The ability to probe and analyze detailed interfacial reactions at buried nylon/silicone interfaces demonstrated that SFG is a powerful analytical technique to aid the design and optimization of materials with desired interfacial properties.

Effect of Surfactant Concentration and Hydrophobicity on the Ordering of Water at a Silica Surface.

The performance of nonionic surfactants is mediated by the interfacial interactions at the solid-liquid interface. Here we applied sum frequency generation (SFG) vibrational spectroscopy to probe the molecular structure of the silica-nonionic surfactant solution interface in situ, supplemented by quartz crystal microbalance with dissipation monitoring (QCM-D) and molecular dynamics (MD) simulations. The combined studies elucidated the effects of nonionic surfactant solution concentration, surfactant composition, and rinsing on the silica-surfactant solution interfacial structure. The nonionic surfactants studied include ethylene-oxide (EO) and butylene oxide (BO) components with different ratios. It was found that the CH groups of the surfactants at the silica-surfactant solution interfaces are disordered, but the interfacial water molecules are ordered, generating strong SFG OH signals. Solutions with higher concentrations of surfactant lead to a slightly higher amount of adsorbed surfactant at the silica interface, resulting in more water molecules being ordered at the interface, or a higher ordering of water molecules at the interface, or both. MD simulation results indicated that the nonionic surface molecules preferentially adsorb onto silanol sites on silica. A surfactant with a higher EO/BO ratio leads to more water molecules being ordered and a higher degree of ordering of water molecules at the silica-surfactant solution interface, exhibiting stronger SFG OH signal, although less material is adsorbed according to the QCM-D data. A thin layer of surfactants remained on the silica surface after multiple water rinses. To the best of our knowledge, this is the first time the combined approaches of SFG, QCM-D and MD simulation techniques have been applied to study nonionic surfactants at the silica-solution interface, which enhances our understanding on the interfacial interactions between nonionic surfactants, water and silica. The knowledge obtained from this study can be helpful to design the optimal surfactant concentration and composition for future applications.

Chain conformation of polymers adsorbed to clay particles: effects of charge and concentration.

High molecular weight polymers are used in industrially important applications where the polymers adsorb onto surfaces of inorganic particles and facilitate dispersion, stabilization or flocculation of formulations. The surface conformation of these adsorbed polymers is key to their performance, yet an understanding of the effects of polymer charge, concentration and molecular weight on polymer conformation is incomplete. Here the adsorption behavior of high molecular weight, non-ionic, polyethylene oxide (PEO) and anionic partially hydrolyzed polyacrylamide (HPAM) polymers to a model clay, LAPONITE® (a trademark of BYK Additives, Inc.), was studied by small angle neutron scattering over a range of polymer concentrations. The adsorption of PEO was dependent on polymer concentration at all molecular weights, first adsorbing onto the radial edge of the clay particles and then to the clay faces as polymer concentration increased. While similar behavior was observed at low concentrations of HPAM, above a critical concentration, HPAM desorption results in large clay aggregates, which decrease in size at higher polymer loadings. The difference in adsorption properties as a function of polymer charge and concentration is interpreted in terms of conformational differences of adsorbed polymer at the clay surface. Changes in the volume fraction of adsorbed PEO with polymer concentration indicate changes in the relative amounts of adsorbed chain segments in trains, loops and tails, with no clay aggregation. In contrast, a constant volume fraction of adsorbed HPAM at low concentrations gives way to desorption at higher concentration due to charge repulsion, and depletion aggregation of the clay.

Observing a Chemical Reaction at a Buried Solid/Solid Interface in Situ.

Chemical reactions are the most important phenomena in chemistry. However, chemical reactions at buried solid/solid interfaces are very difficult to study in situ. In this research, the chemical reaction between two solid polymer materials, a nylon film and a maleic anhydride (MAH) grafted poly(ethylene-octene) (MAHgEO) sample, was directly analyzed at the buried nylon/MAHgEO interface at the molecular level in real time and in situ, using surface and interface sensitive sum-frequency generation (SFG) vibrational spectroscopy. Disappearance of nylon signals indicated a chemical reaction between amine and hydrolyzed amide groups of nylon and MAH groups on the MAHgEO at the buried interface. The appearance of SFG signals from reaction products was also observed at the buried nylon/MAHgEO interface. The mechanism of the observed interfacial reaction was further analyzed. Temperature-dependent SFG experiments were performed to measure the activation energy of the interfacial reaction, enabling a comparison with that reported for the bulk materials. The interfacial chemical reaction between nylon and MAHgEO greatly improved the adhesion of these dissimilar materials. The detailed analysis of a chemical reaction between two polymers at the polymer/polymer buried interface underscores the utility of SFG as a powerful analytical tool to build understanding of buried interfaces and to accelerate the design of interfacial structures with desired properties.

Molecular Insights into Adhesion at a Buried Silica-Filled Silicone/Polyethylene Terephthalate Interface.

Silicone adhesives are widely used in many important applications in aviation, automotive, construction, and electronics industries. The mixture of (3-glycidoxypropyl)trimethoxysilane (γ-GPS) and hydroxy-terminated dimethyl methylvinyl co-siloxanol (DMMVS) has been widely used as an adhesion promoter in silicone elastomers to enhance the adhesion between silicone and other materials including polymers. The interfacial molecular structures of silicone elastomers and the adhesion promotion mechanisms of a γ-GPS-DMMVS mixture in silicone without a filler or an adhesion catalyst (AC) have been extensively investigated using sum frequency generation (SFG) vibrational spectroscopy previously. In this research, SFG was applied to study interfacial structures of silicone elastomeric adhesives in the presence of a silica filler and/or a zirconium(IV) acetylacetonate adhesion catalyst at the silicone/polyethylene terephthalate (PET) interface in situ nondestructively to understand their individual and synergy effects. The interfacial structures obtained from the SFG study were correlated to the adhesion behavior to PET. The interfacial reactions of methoxy and epoxy groups of the adhesion promoter were found to play significant roles in enhancing the interfacial adhesion of the buried interface. This research provides an in-depth molecular-level understanding on the effects of a filler and an adhesion catalyst on the interfacial behavior of the adhesion promotion system for silicone elastomers as well as the related impact on adhesion.

Probing Molecular Behavior of Carbonyl Groups at Buried Nylon/Polyolefin Interfaces in Situ.

Nylon and maleic anhydride (MAH)-grafted polyolefin-based thin co-extruded multilayer films are widely used in packaging applications encountered in daily life. The molecular structure of the nylon/MAH-grafted polyolefin buried interface and molecular bonding between these two chemically dissimilar layers are thought to play an important role in achieving packaging structures with good adhesion. Here, the molecular bonds present at a nylon/maleic anhydride (MAH)-grafted polyethylene buried interface were systematically examined in situ for the first time using sum frequency generation (SFG) vibrational spectroscopy. The carbonyl stretching frequency region of the SFG spectra of a nylon/MAH-grafted polyethylene buried interface showed the presence of hydrolyzed MAH groups grafted to the polyethylene chain and very low levels of unreacted MAH enriched at the buried interface. The ability of SFG to detect these molecular species at the buried interface yields important understanding of the interfacial molecular structure and provides the basis for subsequent in situ studies of the bonding reaction between the grafted MAH and nylon directly at the interface. This understanding may guide the design of multilayer films with improved properties such as enhanced adhesion between polymer layers. The approach used in this study is general and is applicable to study the molecular characteristics of other buried interfaces of significance, such as buried interfaces involving polymers in solar cells, polymer semiconductors, and batteries. Nylon impact modification is another area of interest where the interaction between the MAH-grafted elastomer and the continuous phase of nylon is important.

Structures and Adhesion Properties at Polyethylene/Silica and Polyethylene/Nylon Interfaces.

The molecular structures of buried interfaces of maleic anhydride grafted and ungrafted polyethylene films with silica and nylon surfaces were studied in situ using sum-frequency generation (SFG) vibrational spectroscopy. Grafting maleic anhydride to polyethylene altered the molecular structures at buried interfaces, including changing the orientation of polymer methylene groups and resulting in the presence of C═O groups at silica interfaces. These molecular level changes are correlated with enhanced adhesion properties, with ordered C═O groups and in-plane orientation of the methylene groups associated with higher levels of adhesion. While improved adhesion was observed for grafted polyethylene at the nylon interface, no C═O groups were detected at the interface using SFG, for films thermally treated at 185 °C. In this case, either no C═O groups are present at the interface or they are disordered; the latter explanation is more likely, considering the observed improvement in adhesion.

Effect of formulation conditions on hypromellose performance properties in films used for capsules and tablet coatings.

This study investigated the effects of polymer dispersion and hydration conditions on hypromellose (HPMC) film properties, such as strength, oxygen permeability, water vapor transmission, clarity, and haze. The focus of the study was to build a better understanding of the impact that changes to HPMC dispersion and hydration conditions have on performance properties of the resulting films. This understanding could potentially lead to more flexible formulation guidelines for formulators. Films of HPMC 2906 (USP) were produced from aqueous solutions prepared using various formulation conditions. Results showed that tensile properties and oxygen permeability were not significantly affected by the variables used. The differences observed in water vapor transmission are unlikely to affect practical application of the material. However, the differences observed in clarity and haze at 50°C hydration temperature could affect the appearance of a capsule or coated tablet. Several methods were used to determine whether loss of optical properties was due to surface phenomena or bulk defects within a film. Results indicated that the cloudy appearance was primarily due to surface roughness. Based on this information, there is some flexibility in formulation conditions; however, hydration temperatures greater than 25°C are not recommended.